Hydrogen borrowing provides an efficient and atom economical method for carbon–nitrogen and carbon–carbon bond formation from alcohol precursors. Glycerol is a renewable nontoxic polyol and a potential precursor to small functional organic molecules. We here report the direct amination of solketal, a 1,2-hydroxy-protected derivative of glycerol, via ruthenium-catalyzed hydrogen borrowing, affording up to 99% conversion and 92% isolated yield using [Ru(p-cymene)Cl2]2 as the catalyst precursor. The synthesis of an antitussive agent in 86% overall yield from solketal was also demonstrated using this methodology.